Herbicide

ABSTRACT

Herbicidal substituded amido esters of thiophosphonic acid having the general formula   wherein R is chlorine-substituted C1-C2 alkyl; R&#39;&#39; is straight-chain or branched C1-C4 alkyl; R&#39;&#39;&#39;&#39; is hydrogen, methyl, chloro, or nitro group; Y is a nitro, hydrogen, chlorine, or methyl, provided that R&#39;&#39;&#39;&#39; is not identical with Y and that, when R&#39;&#39;&#39;&#39; or Y is hydrogen, Y or R&#39;&#39;&#39;&#39; can not be chlorine or methyl.

mite 1:1 States einikov et al.

1 Mei 1 1 1 Dec. 2, 1975 HERBICIDE Dm. Ulyanova, 4, korpus A, kv. 96; Artur Felixovich Grapov, Davydkovskaya ulitsa, 10, kv. 106; Tamara Fedorovna Kozlova, Kolomensky proezd, 1, korpus 8, kv. 75, all of Moscow; Galina Borisovna Shakhova, Proletarskaya ulitsa, 8, kv. 20; Valery Pavlovich Pokatun, Tsentralnaya ulitsa 39/7, kv. 11, both of Schelkovo Moskovskoi oblasti; Leonid Dmitrievich Stonov, Lavrushensky pereulok, 17, kv. 21; Ljudmila Alexandrovna Bakumenko, ulitsa Gorkogo, 54, kv. 86, both of Moscow; Tatyana Akimovna Sergeeva, ulitsa Likhacheva 1 1; Lidia Mikhailovna Titova, ulitsa Likhacheva 19, all of Dolgoprudny Moskovskoi oblasti, all of USSR.

[22] Filed: Jan. 6, 1972 [21] Appl. N0.: 215,913

[52] US. Cl. 71/87; 260/954; 260/959 [51] Int. Cl. AOIN 9/36 [58] Field of Search 71/87 [56] References Cited UNITED STATES PATENTS 3,644,600 l/l972 Beriger 1. 71/87 3,652,737 3/1972 Gutman 71/87 3,705,929 12/1972 Schrader ct a1... 71/87 3,819,754 6/1974 Aya et a1. 71/87 Primary Examiner-James 0. Thomas, Jr. Attorney, Agent, or FirmHaseltine, Lake & Waters [57] ABSTRACT Herbicidal substituded amido esters of thiophosphonic acid having the general formula wherein R is chlorine-substituted C -C alkyl;

R is straight-chain or branched C,-C alkyl;

R" is hydrogen, methyl, chlo'ro, or nitro group;

Y is a nitro, hydrogen, chlorine, or methyl, provided that R is not identical with Y and that, when R or Y is hydrogen, Y or R" can not be chlorine or methyl.

2 Claims, N0 Drawings HERBICIDE This invention relates to the use, as herbicides, of

substituted amido esters of alkyl haloalkyl thiophosphonic acids having the general formula having the above formula, can be used as selective herbicides to control weeds in agriculture, in particular to fight millet-like weeds in cereals, for example rice and barley. Propanyl (3,4-dichloroanimide propionate) and molinate (S'ethyl hexamethyleneiminothiolcarbamate), and also isophos (-2,4-dichlorophenyl-N-isopropylamidochloromethyl thiophosphonate) (inventors Certificate of the USSR No. 216380) are used at the present time to control millet-like weeds.

Propanyl is used in the form of a dispersion sprinkled over green plants having 1-3 leaves, the consumption rate of the herbicide being 5 9 kg/hectare. The disadvantage of propanyl is the short period of time during which it can be used and hence the possibility of reinfection of the culture with the weeds at later stages of the plant growth.

Molinate and isophos are pre-emergence herbicides; i.e., preparations that are introduced into the soil before seeding the crops, the dosage being 4-6 kg/hectare. These preparations ensure high efficacy against the millet-like weeds and increase the yields of cereals.

The preferred preparations of this invention, those of, for example, 0-2-chloro-4-methylphenyl-l\l-secondary butylamidochloromethyl thiophosphonate, are more efficaceous, more durable and have a wider spectrum of action compared with the known herbicide 0 2,4-dichlorophenyl-N-isopropylamidochloromethyl thiophosphonate (isophos).

Herbicides according to the present invention can be used for combating weeds in the form of emulsifying concentrates, dusts, wettable powders, and granules.

2 The preparations can be applied either before germination or after the plants have already emerged from the soil. The toxicity of the herbicides with respect to man and warm-blooded animals is moderate.

According to the invention, 0-2-chloro-4-methylphenyl-N-secondary amidochloromethyl thiophosphonate is the most preferred and most active herbicide.

The synthesis of the herbicides of this invention, i.e., the amides of O-arylalkyl (halo alkyl) thiophosphonates can be effected directly from the dichloroanhydride of alkyl (halo alkyl) thiophosphonate by subsequent treat ment with a mixture of one mole of the primary and the secondary amine and one mole of the tertiary amine and finally with a solution ofa substituted phenol in an inert solvent at a temperature from to +10C (method 1), similar to the procedure described in the Inventors Certificate of the USSR No. 228,684.

The said herbicides can be obtained also by the interaction between chloroanhydride of O-aryl-alkyl (haloid alkyl) thiophosphonate and the amine (method [1). (lnventors Certificate of the USSR No. 189.852. 1968).

Method l Empirical analytical data of' the most active herbicides synthesized by the above methods are given in Table 1. For a better understanding of the invention, reference may be had to the following examples, wherein the herbicides of this invention were applied under laboratory and hot-house conditions.

EXAMPLE 1 The herbicidal action of the weed-killers was tested in a laboratory according to the standard procedure. The test plants were grown on agar-agar in Petri dishes. The preparations were introduced into the agar in the form of an aqueous emulsion. The results of the test are gi en in Table 2.

EXAMPLE 2 The herbicidal activity of the weed-killers was tested on wheats, millets, rice, oats, radish. beans, cotton. tomatoes. cucumbers, cabbage. carrots, soya, wild oats, saltbush, barnyard grass.

The herbicidal activity of the weed killer was assessed on a five-grade principle:

0 no affect l very slight affect 2 weak inhibition of plant growth (the growth is arrested, yellow spots develop, 1020 percent loss in weight of green plants 3 marked inhibition of plant growth (-50 percent of plants wither) 4 strong inhibition of plants (-80 percent of plants perish);

4 5 very strong inhibition of plant growth (90-100 as a herbicide on rice and weeds of Echinochloa spepercent of plants perish). cies under hot-house conditions. The preparation was The results of the experiments are given in Table 3. introduced into the soil before seeding. The prepara- EXAMPLE 3 5 non did not produce harmful effect on the r1ce and completely eradicated the weeds. -2-ch1oro-4-methylphenyl-N-secondary The results of the test are given in Table 4.

Table 1 Method of prc- Yield B.p.C N dfi" Nos Compound paru- 71 or m.p.C

tion 1 2 3 4 5 6 7 1. O-Z-nitrophenyl-N-secon- 1 42-43 dary butylamidochloromethyl thiophosphonate 2. O-4-nitrophcny1-Niso- 1 73.4 182/02 1.5830 1.3358

propylamidochloromethyl thiophosphonate 3. O-2-nitm-6-methy1phe- I 68.8 45-46 nyl-N-secondary butylamidochloromethyl thiophosphonute 4. O-2-nitr0-6-methy1phe- 1 7273 nyl-N-secondary butylamidochloromethyl thiophosphonate 5. O-2-chloro-4-nitrophe- 1 63.5. 174/019 1.58 l 6 1.3891

nyl-N-isopropylamidochloromethyl thiophosphonute 6. O-2-chloro-4-ch1orophe- 1 76 163- 1.574 .36 7

nyl-N-secondary butyl 164/017 amidochloromethyl thiophosphonate 7. O-2-nitr0-4methy1phel 55 173- 1.5660 1.3621

nyl-N-secondziry buty1- /025 amidochloromethyl thiophosphonate 8. O-2-ch1oro-4-methylphe- 1 66 147/017 1.5558 1.2310

nyl-N-secondary butylamidochloromethyl thiophosphonate 9. O-2-methyl-4-chlorophe- 1 70.2 137- 1.5619 1.2220

ny1-N-isopropylamido 138/012 chloromethyl thiophosphonate 10. O-2-ch10ro4-methylphe- 11 85.7 51.5-53

nyl-N-methylamidochloromethyl thiophosphonate Found. 7: Empirical Calculated. 7r N Cl P S formula N Cl P S 8 9 10 1 1 12 13 14 15 16 8.54 0.87 C H CIN O PS 8.68 9.60 8.60 9.58 9.16 10.59 C H C1N O;,PS 9.07 10.39 9.21 10.75 8.66 10.02 C H CIN O PS 8.68 9.94 8.69 10.05 8.60 9.22 C H ClN O- PS 8.32 9.20 8.58 9.50 8.16 9.32 C H Cl N o Ps 8.16 9.63 8.36 9.51 7.74 19.88 C H Cl N O PS 7.84 19.85 7.92 19.92 8.60 9.05 C H C1N O PS 8.32 9.20 8.55 8.82 4.44 21.60 9.68 C H CI NOPS 4.29 21.74 9.83 4.59 21.84 9.55 4.60 22.91 C H CENOPS 4.49 22.71 4.59 23.19 4.51 25.14 11.00 C H CI NOPS 4.43 24.96 10.90 4.48 24.97 11.23

butylamidochloromethyl thiophosphonate was tested 11. O-2-ch1oro-4-methy1phe- 11 90.3 138- 1.5742 1.3179

nyl-N-dimethylamido- 139/0.15 chloromethyl thiophosphonate l2. O-2-chloro4-methylphe- 11 84.6 141/0.16 1.5723 1.2994

nyl-N-ethylamidochloromethyl thiophosphonate 13. O-2-chloro-4-methylphe- 11 83.5 132- 1.5642 1.2638

Table 2-continued Nos Compound Dose (in kg/hectare) producing 50 per cent inhibition wheat oats millet shoots roots shoots roots shoots roots shoots roots radish O-Z-nitrophenyl-N-secondary butylamidochloromethyl thiophosphonate O-2-nitro-4-methylphenyl-secondary butylamidochloromethyl thiophosphonate O-Z-nitro-t'v-methylphcnyl-N-secondary butylamidochloromethyl thiophosphonate O-2-nitro-4-chlorophenyl-N-secondary butylamidochloromcthyl thiophosphonate O-2-chloro-4-nitrophenyl-Nisopropylamidochloromethyl thiophosphonate O-2-chloro-4-nitr0phcnyl-N-secondary butylamidochloromethyl thiophosphonate O-2-methyl-4-chlorophenyl-N-isopropylamidochloromethyl thiophosphonate O-2-methyl-4-chlorophenyl-N-isopropylamidochloromethyl thiophosphonute l 0.007 0.8 0.005 0.35 0.008 l l l 0.008 l 0.005 l 0.3 l l Table 3 Nos Preparation Rad- Cot- Toish Bean ton mato Cul- Milture Wheat Oats let Rice O-2-nitro-4-chlorophenyl-N-secondary butylamidochloromethyl thiophosphonate O-2-chloro-4-nitrophenyl-N-isopropylamidochloromethyl thiophosphonate O-2-chloro-4-methylphenyl-N-isopropylamidochloromethyl thiophosphonate 0-2-chloro-4-methylphenyl-N-secondary butylamidochloromethyl thiophosphonate Table 4 Saltbush Cab- Carbagc Cucum- Barnyard Wild bers grass oats O I l 0 We claim: l. A herbicidal composition comprising as an active Nos Compound O-2-chloro-4-methylphenyl-N-secondary butylamidochloromethyl thiophosphonate Controls Herbicidal activity (S-degree scale) kg/ha rice millet rice Dose in butylamidochloromethylthiophosphonate. 

1. A HERBICIDE COMPOSTION COMPRISING AS AN ACTIVE INGREDIENT AN EFFECTIVE AMOUNT OF THE COMPOUND O-(2-CHLORO-4METHYLPHENYL)-N-SEC.-BUTYLAMIDO CHLOROMETHYLTHIOPHOS
 2. A method of controlling weeds comprising applying to said weeds an effective amount of a herbicidal composition comprising as an active ingredient the compound 0-(2-chloro-4-methylphenyl)-N-sec.-butylamido-chloromethylthiophosphonate. 